Inhibiting the gas fading of dyed acetate silk



Patented Sept. 9, 1941 mmnrrma 'rrm GAS FADING F DYED ACETATE smx JohnM. Tinker and Donovan E. Kvalnes, Perms Grove, N. J., assignors to E. Ldu Pont de Nemours & Company, Wilmington, Del., a corporation ofDelaware No Drawing. Application February 13, 1940, Serial No. 318,706

7 Claims.

This invention relates to improvements in dyed cellulose acetate fibers,and especially to the prevention of fading which results when such dyedfibers are exposed to deleterious fumes, such as atmosphere whichcontains oxides of nitrogen or sulfur.

When dyed articles of cellulose acetate fibers are stored where they areexposed to atmosphere containing oxides of nitrogen and sulfur it hasbeen observed that the dyeings change shade and lose strength. Fading isproduced more or less rapidly by the action of various concentrations ofthe deleterious gases. Even in minute concentration, the deleteriousgases are effective, as for example where the dyed goods are stored orexposed for a considerable period of time to an atmosphere whichcontains such small amounts of the deleterious oxides. It is thereforedesirable to provide dyed cellulose acetate fibers so that they willhave good fastness to dry cleaning and washing and will resist theaction of deleterious gases. Means for such purposes are desired whichwill not have a harmful effect on the shade or fastness properties ofthe dyes.

It is among the objects of the invention to provide means to inhibit theaction of such deleterious gases on dyed cellulose acetate fibers.Another object of the invention is to provide inhibitors which do notdeleteriously affect the shade and fastness of the dyes and which willgive effective protection after the goods are cleaned. Other objects ofthe invention will be apparent from the following description.

The objects of the invention are attained in general by afiixing to thefibers certain biguanides. These may be conveniently applied or affixedto the fibers by wetting or saturating the dyed fibers with a watersolution or suspension of the inhibitor and then removing the water.

The invention will be more fully set forth in the following moredetailed description which includes examples that are given asillustrative embodiments of the invention and not as limitationsthereof. Parts are expressed in parts by weight unless otherwise noted.

Example I One-half to two parts of phenyl biguanide were dissolved in100 parts of water by gentle warming and stirring. Five parts ofcellulose acetate silk which had been dyed with 1,4- di(mono methylamino) anthraquinone were immersed for a period of from 30 seconds tothree minutes in the solution of phenyl biguanide. The solutiontemperature was between 25 and 100 C. The acetate rayon was removed anddried.

On exposure to the fumes of a gas burner and to atmosphere containingoxides of nitrogen, the

larly treated with ortho tolyl biguanide, like results were produced.

Example II One part of phenyl biguanide was intimately mixed into awater solution containing one-half part of soap. Five parts of celluloseacetate silk dyed with 1,4,5,8-tetra-amino anthraquinone were enteredand saturated in the dispersion which was held at 70 C. After fiveminutes, the saturated material was removed, rinsed and dried. Uponexposure to an atmosphere containing oxides of nitrogen, it remainedunchanged while an untreated dyeing of the same kind faded to aconsiderable extent.

Similar results were obtained by using phenyl, ethyl biguanide insuspension instead of phenyl bi uanide.

Example III Cellulose acetate fabrics dyed with the azo dye representedby the formula were severally treated with phenyl biguanide and orthotolyl biguanide similarly to the treatment described in Example I andsimilar protection from gases containing oxides'of nitrogen and sulfurwas obtained.

These treatments gave good protection to dye ings on'acetate silk whichwere dyed with the following compounds:

r m, com I NHCOCH;

' and A large number of biguanides can be used in accordance with theinvention and with the effect described in the foregoing examples. Suchbiguanides, sometimes called blguanidines .o'r guanyl guanidines may bereadily prepared by reacting a primary or secondary amine with dicyandiamide in the manner described in Jour. fi;:. prakt. Chem., 84, 396,thereby producing biguanides of the general formula 1 m H wherein R ishydrogen or the substituted group of the secondary amine. Mono-, bisor-trisbiguanides are produced when one, two or three groups are presentin the nucleus. Accordingly aniline produces all of which have thedescribed effect of the biguanides mentioned in the foregoing examples.As illustrative of the class of biguanides which are useful for thepurposes of the present invention and which may be produced in likemanner from arylamines and heterocyclic amines, the following amines arementioned as the starting materials from which such representativebiguanides are made; aniline, o, m and p-toluidines, xylidines,cresidine, 2,5-dimethoxy aniline, monoand di-chlor anilines, o, m andp-cyano aniline, m-amino benz'otrifluoride, 0, m and pamino phenylmethyl sulfone, o, m and p amino acetophenone, p-amino phenyl.beta-hydroxy ethyl ether, 0, m and p-anisidine and phenetidine,p-dodeoyl aniline, p-amino ethyl benzoate, sulfanilamide, p-aminoacetanilide, o, m and pphenylene diamine, m-toluene diamine, 2,4-diaminoanisol, 2,4-diamino chlorbenzene, benzidine, toluidine dianisidine,2,4,4'-triamino diphenyl, 1,3,5-triamino benzene, 2,4,6-triaminotoluene, 4,4-diamino diphenyl ether, thioaniline, 4,4-diamino diphenylsulfone, 4,4'-diamino diphenyl urea, p-amino benzoyl m-phenylenediamine, m-amino benzoyl p-phenylene diamine, m-amino benzene sulfonylm-phenylene diamine, 4,4'-diamino stilbene,1,2-di(4,4-amino-phenoxy)ethane, l,2-di(3-amino phenyl) ethane, 4,4- diamino diphenyl amine,4,4'-diamino diphenyl methane, 4,4'-di(mono ethyl amino) diphenylmethane, m-amino phenyl methyl pyrazolone, 2- aminol-methyl thiazol,2-amino benzothiazol, amino tetrazol, 2- and 3-amino pyridine, 2,6-dia-mino pyridine, 2,4,6-triamino pyridine, alpha andbeta-naphthylamine, 2-methoxy-l-naphthylamine, 4-amino N-methyl naphthostyril, amino antipyrene, N -methyl aniline, N-ethyl aniline, N- hydroxyethyl aniline, N-butyl aniline, N-methyl o-toluidine, n-methyl aniline,hydroxy propyl aniline, hydroxy amyl aniline, 2-hydroxy-3 chlor-propylaniline, 4-amino-diphenyl sulfone and 4-amino diphenyl.

Accordingly, the compounds useful as inhibitors are the mono-, bisandtrisbiguanides which may be represented by the formula in which thenuclear radical R is from the benzene, naphthalene or heterocyclicseries and the series of diphenyl compounds represented by the formulain which X is one of a group consisting of --O-, -S-, NH, CH2SO2-, CO,-CH:CH2, -CH=CH, NHCO-, N'HCONH, OCH2CHzO--, and NHSO:; and p is aninteger not greater than 2. In cases where p is 1, the radical has nobridging group. Any of these nuclei may be unsubstituted or substitutedonce to twice by any combination of alkyl groups having 1 to 12 carbons,methoxy, ethoxy, CFa, halogen, COCH3, CN, acetylamino, -SO2CH3 and SO2phenyl. The diphenyl compounds can be substituted in each benzene ring.In the above formula m is 1 to 3 and R is one of a group consisting ofhydrogen, alkyl having 1 to 5 carbons and hydroxyalkyl havingl to 5carbons. The biguanides of the benzene series arethe preferredembodiments, such as those represented by the formula wherein Arepresents the nuclear substituents heretofore recited and n is 1 or 2,and of these the mono-biguanides are preferred.

The biguanides used in carrying out the invention have good afiinity forcellulose acetate fibers resulting in rapid absorption and goodretention by the fiber, but the precise reasons for their inhibitingaction are not fully understood. It has been suggested that theinhibiting effect may be due to the formation of salts or oxides by theaction of the deleterious fumes on the biguanides in preference to asalt forming or oxidizing action on the dye. The nature of the reactionproducts is not fully known and it is to be understood that theinvention is not limited by the proposed theory.

The invention is especially useful in improving the properties of dyedcellulose acetate fibers which are dyed with the anthraquinone and themonazo dyes, such as 1,4 di[mono hydroxy ethyl amino] anthraquinone,l-methyl amino-a-hydroxy ethyl amino anthraquinone, l-amino-4- methylamino anthraquinone, 1,4-diamino-5- nitro anthraquinone,l-amino-4-anilidoanthra quinone and 4-amino-4-nitro-azobenzene withwhich a similar degree of protection is afforded by the biguanidesdescribed.

It is commonly preferable to apply the biguanides as an after treatmentto the dyed fiber but it may be applied during the dyeing operation byadding the inhibiting compound to the dyebath or other treating bath.Any manner of aifixing or adsorbing the inhibitor on and in the fibergives beneficial results. A short immersion of the fibers, such as aboutthirty secends is frequently sufficient to give adequate protection butbetter results are sometimes obtained with longer immersions, such asthree to five minutes. The adsorption of the inhibitor varies somewhatwith the various circumstances but it is generally quite rapid.Considerably longer immersions than those mentioned can be employed whenthey are desired since they are not harmful, but such excessively longimmersions are commonly unnecessary. The best duration of time forimmersing the fibers may vary somewhat depending on circumstances, suchas the particular inhibitor used, the character and condition of thefiber acter of the treating'bath. The wide variation permissible in thetreatment is adanta eous since it lends itself desirably to the specialcircumstances encountered in practice. The fastness of the dyeings isnot adversely affected and in most cases it is improved.

From the foregoing disclosure it will be recognized that the inventionissusceptible of modification without departing from the spirit and scopethereof and it is to be understood that the invention is not restrictedto the specific illustrations herein set forth.

We claim:

1. A dyed article of cellulose acetate fibers which has affixed to saidfibers a biguanide of a group represented by the formula in which R is anucleus of the benzene, naphthalene heterocyclic and (an (A) series, mis 1 to 3; R is one of a group consisting of hydrogen, alkyl having 1 to5 carbons and hydroxyalkyl having 1 to 5 carbons; A is from the groupconsisting of hydrogen, alkyl having 1 to 12 carbons, methoxy, ethoxy,CFa, halogen, COCHa, CN, acetylamino, SOzCHa and SO: phenyl; n is aninteger not greater than 2; X is one of a group consisting of -O-, -S-,NH, CH2SO2, CO-, CH2CH2-, -CH=CH, NHCO--, NHCONH-, OCHaCHaO- and NHSO2-;and p is an'integer not greater than 2.

2. A dyed article of cellulose acetate fibers which has affixed to saidfibers phenyl biguanide.

3. A dyed article of cellulose acetate fibers which has aifixed to saidfibers phenyl ethyl biguanide.

4. In the process of inhibiting the action of gases which aredeleterious to dyeings on cellulose acetate fibers, the steps whichcomprise wetting the dyed fibers with an aqueous fluid containing abiguanide and then'removing the water so as to affix the biguanide tothe fibers, said biguanide being represented by the formula and,thetemperature and char-.

in which R is a nucleus of the benzene, naphthalene, heterocyclic anddo. n

series, m is i to 3; R is one of a group consisting of hydrogen, alkylhaving 1 to 5 carbons, hydroxyalkyl having 1 .to 5 carbons; A is fromthe group consisting of hydrogen, alkyl having 1 to 12 carbons, methoxy,ethoxy, CFc, halogen, COOCI-Is, CN, acetylamino, SOzCHa and -SO2 phenyl;n is an integer not greater than 2; X is one of a group consisting of-O-, S-, NH-, CH2SO2-, CO-, CH2CH2-, CH=CH-, -NHCO-, NHCONH-,--OCH2CH2O, and NHSO2-; and p is an integer not greater than 2.

5. In the process of inhibiting the action of gases which aredeleterious to dyeings on cellulose acetate fibers, the steps whichcomprise saturating the dyed fibers with an aqueous fluid containing abiguanide and then removing the water so as to affix the biguanide tothe fibers, said biguanide being represented by the formula in which Ris a nucleus of the benzene, naphthalene, heterocyclic and series, m is1 to 3; R is one of a group consisting of hydrogen, alkyl 'having 1 to 5carbons, hydroxyalkyl having 1 to 5 carbons; A is from the groupconsisting of hydrogen, alkyl having 1 to 12 carbons, methoxy, ethoxy,CFz, halogen, COOCHa, CN, acetylamino, SOzCHs and -SO2 phenyl; n is aninteger not greater than 2; X is one of a group consisting of -O-, -S,NH--, --CH1SOz-, C0, CH2CH2-, NHCO-, NHCONH-, -OCH2CH20- and NHSO2; andp is an integer not greater than 2.

6. In the process of inhibiting the action of gases which aredeleterious to dyeings on cellulose acetate fibers, the steps whichcomprise wetting the fibers with an aqueous fiuid containing phenylbiguanide and-then removing the water, thereby to affix said biguanideto the fibers.

- '7. In the process of inhibiting the action of gases which aredeleterious to dyeings on cellulose acetate fibers, the steps whichcomprise wet ting the fibers with an aqueous fluid containing phenylethyl biguanide.

' JOHN M. TIN'KER.

DONOVAN E. KVALNES.

